Wang Dingyi, Zhao Yunfei, Yuan Chengkai, Wen Jian, Zhao Yue, Shi Zhuangzhi
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Angew Chem Int Ed Engl. 2019 Sep 2;58(36):12529-12533. doi: 10.1002/anie.201906975. Epub 2019 Jul 30.
A rhodium-catalyzed system is introduced for in situ modification of biaryl-type monophosphines with hydrosilanes through a P -chelation-assisted dehydrogenative silylation reaction. A series of ligands containing silyl groups with different steric and electronic properties were obtained with excellent regioselectivities. This method offers many advantages, including the use of commercially available phosphines, no requirement for an external ligand or oxidant, a broader substrate scope, high efficiency, and access to a single regioisomer. Based on the outstanding properties of the parent scaffolds, the silyl-substituted phosphines serve as excellent ligands in Pd-catalyzed asymmetric Suzuki coupling reactions.
介绍了一种铑催化体系，用于通过P-螯合辅助的脱氢硅烷化反应，用氢硅烷对联芳基型单膦进行原位修饰。获得了一系列具有不同空间和电子性质的含硅烷基的配体，区域选择性优异。该方法具有许多优点，包括使用市售的膦，无需外部配体或氧化剂，底物范围更广，效率高，并且能够得到单一的区域异构体。基于母体骨架的优异性能，硅烷基取代的膦在钯催化的不对称铃木偶联反应中作为优异的配体。
